CN1854277A - Process for producing fat or oil - Google Patents
Process for producing fat or oil Download PDFInfo
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- CN1854277A CN1854277A CNA2006100781779A CN200610078177A CN1854277A CN 1854277 A CN1854277 A CN 1854277A CN A2006100781779 A CNA2006100781779 A CN A2006100781779A CN 200610078177 A CN200610078177 A CN 200610078177A CN 1854277 A CN1854277 A CN 1854277A
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- China
- Prior art keywords
- distillation
- oil
- grease
- reaction
- monoacylglycerol
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Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
Abstract
A method for producing a diacylglycerol-rich fat or oil is provided. This method includes the steps of reacting an acyl group donor with an acyl group receptor, and separating unreacted material and byproducts by distillation for use as a part of the starting material in the subsequent cycle of production. The distillation is conducted such that the content of monoacylglycerol in the fat or oil after the distillation is 0.5 to 15% by weight.
Description
Technical field
The present invention relates to the high greasy manufacture method of a kind of DG content.
Background technology
Physiological actions (Japanese kokai publication hei 10-176181 communique) such as the grease that contains the high density DG, the known savings that has in vivo lack are widely used as edible oil.The manufacture method of DG is known to be had; carry out the method (Japanese kokai publication hei 1-71495 communique) of esterification as raw material by chemical method or enzyme process with lipid acid and glycerine, carry out the method etc. (international No. 03/29392 brochure, the Japanese kokai publication sho 63-133992 communique of disclosing) of glycerolysis with grease and glycerine as raw material by chemical method or enzyme process.
In addition, the high density ground by this method manufacturing contains in the grease of DG, contains lipid acid, monoacylglycerol, distinguishing the flavor of becomes to grade impurity.For the grease that high density ground contains DG is used as edible oil, must make local flavor become good by reducing these impurity.
Contain in the greasy manufacture method of DG on high density ground, when having grease after reaction is finished refining, the technology (Japanese kokai publication hei 8-294394 communique) that the monoacylglycerol that reclaims is added as the raw material of next reaction.This technology is that the monoacylglycerol that reclaims when impurity as edible oil is removed in distillation under high vacuum condition adds in next reaction system, is the technology of purpose by the solubleness that improves the glycerine of lipid acid in mutually with the speed that improves esterification.In addition; also having with grease and glycerine is raw material; when carrying out glycerolysis, glycerine remaining in the reaction system and monoacylglycerol are reclaimed with wet distillation or with molecular distillation, use the technology (the international brochure that discloses No. 03/29392) in next reaction again by chemical method.This technology does not need the such operation of esterification after in a single day grease is decomposed into lipid acid, so good economy performance.In addition, also having to retain trace ingredients such as plant sterol in the DG product is purpose, does not distill after part adds the water decomposition grease and carries out the technology (Japanese kokai publication hei 11-123097 communique) of esterification.Though this technology is outstanding on trace ingredients this point such as retention plant sterol,, the concentration of the DG of generation is low, in addition, does not also consider the recycling to unreacting substance and by product.
Summary of the invention
The invention provides the greasy manufacture method that a kind of high density ground contains DG; it is after making confession acyl group material and being subjected to the acyl group substance reaction; by fractionation by distillation unreacted reactant and by product; and the high density ground that this distillation fraction re-uses as the part of reaction raw materials is contained the greasy manufacture method of DG; it is characterized in that the monoacylglycerol content in the grease after the feasible distillation is 0.5～15 weight %.
Embodiment
In recent years, society is more and more higher to the requirement of environmental problem, more and more wish to occur taking into account the manufacturing of high-quality product and has reduced manufacturing technology to the load of environment.In order to reduce carrying capacity of environment, effective means is the amount that reduces the waste of discharging from manufacturing process.Wish to occur a kind of like this technology, it for the material that can utilize again in the material that is removed, does not discharge as waste when containing the grease of DG with making high density, and with its recycling.
In above-mentioned prior art, when making high density ground and contain the grease of DG, need remove as edible oil be the lipid acid, the monoacylglycerol that are not suitable for composition, distinguishing the flavor of becomes to grade.But, when the operation of removing these compositions, be present in vitamin-E in the raw oil material, plant sterol etc. and the useful one-tenth of organism is graded also can be removed.In addition, as previously mentioned, proposed when making high density ground and contain the grease of DG, to reclaim remaining glycerine and monoacylglycerol in the reaction system, it has been used technology in next reaction again with wet distillation or molecular distillation.But it does not solve following problem: owing to carrying out with the high vacuum being the molecular distillation of prerequisite, be removed from greasy useful component; Because hot resume are long, promoted the generation to the bad trans unsaturated fatty acids of organism.In addition, above-mentioned part adds does not distill after the water decomposition grease and carries out the technology of esterification, because the amount of waste is many, carrying capacity of environment is big, also has the not good enough shortcoming of economy.In addition, even unreacted reactant and by product are carried out recycling, owing to be that part is decomposed, its rate of decomposition is low, the concentration of the DG of product is low, and the amount of reacted unreacted reactant and by product is many, and yield is also and then many, and efficient is not high.
DG is because a little less than the hydrophobicity than triacylglycerol, with the affinity height of lipid acid, monoacylglycerol, has and is not easy character that they are removed.So; though in order to remove impurity, to improve the purity of DG and as the refining degree of edible oil; preferably under the condition of strictness, carry out; but then, found the generation because of the trans unsaturated fatty acids of high thermal process, the purity that produces because of the reaction of homogenizing not decline, from raw oil material to unfavorable one sides such as being removed of the useful composition of organism.
So; the purpose of this invention is to provide a kind of; contain in the grease of DG on high density ground; when improving the purity and refining degree of DG, make in the raw oil material the useful composition of organism to be remained in oil and fat product, that carrying capacity of environment is little and economical efficiency is good, as to contain the high density DG greasy manufacture method as edible oil.
The inventor has carried out all research to the greasy manufacture method that contains the high density DG; and find: by reacted distillation condition is set in specific scope; and utilize the cut that reclaims by distillation again; can suppress the generation of trans unsaturated fatty acids; and can keep useful components such as plant sterol here from raw oil material; simultaneously, can also improve the content of DG.
In the present invention; supply the acyl group material as the employed raw material of method of the present invention; can enumerate the triacylglycerol of rapeseed oil, soybean oil, sunflower seed oil, plam oil, flaxseed wet goods vegetables oil or animal oil such as tallow, fish oil, add the low-carbon-ester of the resulting lipid acid of these greases of water decomposition or these lipid acid in addition.Wherein, there is not the good aspect of gonorrhoea outward appearance to consider, the vegetables oil that preferred unsaturated fatty acid content is high or it is added the lipid acid that water decomposition obtains, wherein more preferably rapeseed oil, soybean oil or it is added the lipid acid that water decomposition obtains from physiologic effect, product.Can use separately for the acyl group material, also can make up more than 2 kinds and use.Content for the unsaturated fatty acids in the acyl group material integral body is preferably 60 weight % above (following be expressed as simply " % "), particularly preferably in more than 70%, more preferably more than 80%.Monoenoic acid in the unsaturated fatty acids is preferably 10～80%, and more preferably 15～70%, diolefinic acid is preferably 10～80%, and more preferably 15～60%, trienic acid is preferably 0.2～70%, and more preferably 0.5～60%.When use supplied the acyl group material more than 2 kinds, the content of these unsaturated fatty acidss was the content in their total meterings.Can enumerate glycerine as being subjected to the acyl group material.
In the present invention, the greasy manufacture method that contains DG as high density ground, can enumerate: with as for the lipid acid that adds the above-mentioned grease gained of water decomposition of acyl group material or the ester of these lipid acid and lower alcohol, with the glycerine that is subjected to the acyl group material be raw material, carry out the method for esterification by chemical method or enzyme process; Perhaps, to be raw material with being subjected to the glycerine of acyl group material, carry out the method for glycerolysis by chemical method or enzyme process as above-mentioned grease for the acyl group material.Wherein, from the purity aspect consideration that DG is formed and improved to the lipid acid that can adjust product, preferably carry out the method for esterification with lipid acid and glycerine.In addition, consider, preferably carry out esterification by enzyme process from the purity aspect of the generation that suppresses trans unsaturated fatty acids, the lipid acid composition that can adjust product, raising DG.In addition, under the situation of the product that obtains the lipid acid composition close, consider the method for passing through glycerolysis of preferred grease and glycerine from the aspect that can simplify manufacturing process with raw oil material.In addition, from shortening the reaction times, improving the consideration of productive aspect, preferably carry out the method for glycerolysis by chemical method; And consider from the generation aspect that suppresses trans unsaturated fatty acids, preferably carry out the method for glycerolysis by enzyme process.
In the present invention, grease is preferably, respectively after the plant or animal oil expression that become raw material, remove oil content solids component in addition with filter or centrifugation etc., add water, according to circumstances add acid again and mix after, separate gum component by centrifugation etc., implement to take off natural gum and handle.In addition, after preferably adding alkali and mixing, carry out depickling by washing and handle.Further, the processing of preferably decolouring, that is, and after making it and sorbent materials such as atlapulgite contacting, by the filtering separation sorbent material.These processing are preferably carried out according to above order, but also can change its order.In addition, divide, also can carry out (Wintering/ ゥ ィ ソ リ ソ グ) processing of surviving the winter of separate solid branch at low temperatures in order to remove filter.Further, it is contacted with water vapour and carry out the deodorization processing.At this moment, consider that from the viewpoint of the generation that suppresses trans unsaturated fatty acids preferably reduce hot resume, the temperature during deodorization procedures preferably is controlled at below 300 ℃, especially preferably is controlled at below 270 ℃ as far as possible.In addition, the time of deodorization is preferably below 10 hours, particularly preferably in below 5 hours.
In the present invention, trans unsaturated fatty acid content aspect from reduce the finished product is considered, trans unsaturated fatty acid content in the raw oil material integral body used in the present invention is preferably below 1.5%, more preferably below 1%, particularly preferably in below 0.5%.Here, when using more than 2 kinds grease, trans unsaturated fatty acid content is the content in their the total amount.In addition, to the mensuration of the trans unsaturated fatty acid content in the formation lipid acid of raw oil material, can be undertaken by American Oil Chemists.Society Official Method Ce 1f-96 (GLC method).
In the present invention, when the esterification manufacturing by lipid acid and glycerine contains the grease of high density DG, before esterification, carry out the water decomposition that adds of raw oil material earlier.The water decomposition that adds of raw oil material can be high-pressure decomposing method or enzyme decomposition method, also can make up the two and carry out.Consider from the content aspect that reduces trans unsaturated fatty acids as far as possible, preferably raw oil material is added water decomposition by the low enzyme decomposition method of hot resume.In addition, when adding water decomposition, from the local flavor of the form and aspect of the lipid acid that obtains or glyceryl ester and make form and aspect become viewpoints such as high-quality, preferably raw oil material added water decomposition by the high-pressure decomposing method more than 30% with the high-pressure decomposing method.Further, when reducing trans unsaturated fatty acids, make local flavor and form and aspect become aspect such as high-quality and consider, preferably 35～95%, preferred especially 40～90% of raw oil material is added water decomposition by the high-pressure decomposing method.
In addition, when the content of the trans unsaturated fatty acids of the formation lipid acid in the raw material originally when high, consider that from the content aspect that does not increase the trans unsaturated fatty acids gained lipid acid or the grease as far as possible the water decomposition that adds of raw oil material is preferably undertaken by the enzyme decomposition method; When the content of the trans unsaturated fatty acids of the formation lipid acid in the raw material is low, consider that from efficient, local flavor, the form and aspect aspect of operation the water decomposition that adds of raw oil material is preferably undertaken by the high-pressure decomposing method.As the material that adds water decomposition by the high-pressure decomposing method, the content of the trans unsaturated fatty acids in the greasy formation lipid acid of preferred feedstock is below 1%, more preferably below 0.8%, particularly preferably in below 0.5%.
In addition, because the degree of unsaturation of the formation lipid acid of raw oil material is high more, easy more because of heating causes transization, so the grease that contains the high lipid acid of more degree of unsaturation preferably adds water decomposition with the enzyme decomposition method.Particularly, degree of unsaturation is that transization takes place the heating of 1 oleic acid hardly, and degree of unsaturation to be 2 transization when above will become remarkable.So, contain degree of unsaturation and be more than 2 formation lipid acid more than 40%, further more than 50%, special in the raw oil material more than 60%, preferably add water decomposition with the enzyme decomposition method.In addition, high transization is remarkable more more owing to degree of unsaturation, so, contain degree of unsaturation and be the raw oil material of formation lipid acid more than 10% more than 3, preferably add water decomposition with the enzyme decomposition method.
The water decomposition that adds that the high-pressure decomposing method is preferred uses 220～270 ℃ high-pressure water heating to come raw oil material carried out usually 2～6 hours.Consider that from the generation aspect that suppresses trans unsaturated fatty acids the preferred low temperature of temperature is considered the preferred high-temperature of temperature from the aspect of shortening reaction times, simplification high pressure reaction assembly.The temperature of high-pressure water heating is more preferably at 225～265 ℃, further preferably at 230～260 ℃, particularly preferably in 235～255 ℃.In addition, for same consideration, the time is preferably 2～5 hours, more preferably 2～4 hours.
As employed grease decomposition enzyme, preferred fat enzyme in the enzyme decomposition method.Lipase can directly use from animal, from the enzyme of plant, also can use the commercially available lipase from microorganism.
Add water decomposition and there is no need to proceed to rate of decomposition and reach 100%, can select best rate of decomposition.Here the so-called water decomposition rate that adds is meant the acid value/saponification value of decomposing oil.The load aspect that adds the water decomposition operation from minimizing considers, under the situation of high-pressure decomposing method rate of decomposition preferably 67～98%, more preferably 75～96%, further preferably 80～95%, particularly preferably in 83～95%, especially preferably 90～94%; Rate of decomposition is preferably 50～98% under the situation of enzyme decomposition method, and more preferably 67～96%, further preferably 75～94%, particularly preferably in 80～92%, especially preferably 85～90%.By making rate of decomposition is above-mentioned scope, can make the size appropriateness of the device that adds the water decomposition operation, and can shorten the time of esterification, can also suppress the deterioration of the quality that causes because of heat or the increase of trans unsaturated fatty acids.In addition, the purity of the finished product DG can be remained on high level.In addition, from the concentration aspect of the DG that improves product, the cut amount that is recovered by reacted distillation can reduce, preferred rate of decomposition height is considered in the aspect that can reduce to reclaim the load that re-uses.
The lipid acid that adds the water decomposition gained can directly use, also can use make with extra care, undertaken by passing the winter etc. the adjustment that lipid acid forms by distillation after.
Lipid acid and glycerine are carried out esterification method or grease and glycerine carried out the method for glycerolysis, can use among chemical synthesis, the enzyme process any one, but the content aspect that never increases the trans unsaturated fatty acids in the final oil and fat product is considered, preferably uses enzyme process.
As esterification or the employed enzyme of glycerolysis, preferably use lipase.Particularly; with functional greases such as DG be fabricated to purpose the time; can enumerate, be easy to optionally that the head mold of synthesis of diacyl glycerine (Rizopus) belongs to, aspergillus (Aspergillus) belongs to, Mucor (Mucor) belongs to, pseudomonas (Pseudomonas) belongs to, a silk bacterium (Geotrichum) belong to, Penicillium notatum (Penicillium) belongs to, candidiasis (Candida) belongs to etc.
In addition, the employed enzyme of esterification or glycerolysis is considered from the cost aspect, the preferred enzyme that has been cured that uses.
When carrying out esterification or glycerolysis, consider preferred 0～100 ℃ of temperature of reaction, more preferably 20～80 ℃, preferred especially 30～80 ℃ from the aspect of the inactivation that improves speed of response and inhibitory enzyme with enzyme process.
When carrying out esterification or glycerolysis, consider preferred 100～300 ℃ of temperature of reaction, more preferably 150～250 ℃ from the generation aspect that improves speed of response and the trans unsaturated fatty acids of inhibition with chemical method.In addition, from improving speed of response, the good aspect of form and aspect of reaction oil being considered, preferably use the acid of the alkali of sodium hydroxide, calcium hydroxide etc. or organic acid etc. or its salt as catalyzer.
When carrying out esterification with enzyme process, consider from the content aspect of the DG that improves reaction oil, carry out processed by decompression during preferred reaction.When carrying out esterification with chemical method, consider from the content aspect of the DG that improves reaction oil, carry out processed by the circulation carrier gas during preferred reaction.
Raw material input amount when carrying out esterification or glycerolysis; become the best (lipid acid the reaction oil and the remaining quantity of glycerine from the reaction oil composition; and; the growing amount of monoacylglycerol or triacylglycerol is suppressed; the content of DG increased when the distillation load reduced; the formation efficiency height) aspect is considered; preferably the ratio with respect to the fatty acid-based mole number of glyceryl mole number is 0.2～10; more preferably 0.3～8; be preferably 0.5～6 especially, especially be preferably 0.5～4.Below, represent this ratio with " FA/GLY " with respect to the fatty acid-based mole number of glyceryl mole number.FA/GLY can represent with following formula.
FA/GLY=(mole number * 3 of the mole number of the mole number+DG of the mole number+monoacylglycerol of the low-carbon-ester of the mole number+lipid acid of lipid acid * 2+ triacylglycerol)/(mole number of the mole number+triacylglycerol of the mole number+DG of the mole number+monoacylglycerol of glycerine)
FA/GLY can suitably select according to the reaction form.For example, when using enzyme to carry out esterification or glycerolysis, become best aspect from the reaction oil composition and consider that its value is preferably 1～3, more preferably 1.5～2.5.When carrying out esterification or glycerolysis, become best aspect from the reaction oil composition and consider that its value is preferably 0.3～3, more preferably 0.4～2.2 with chemical method.
In having carried out the reaction oil after the esterification, unreacted reactant lipid acid and glycerine, by product triacylglycerol and monoacylglycerol are arranged with DG is simultaneous.
In having carried out the reaction oil behind the glycerolysis, unreacted reactant glycerine and triacylglycerol, by product monoacylglycerol are arranged with DG is simultaneous.
Having carried out content after the esterification or that carried out the monoacylglycerol in the reaction oil behind the glycerolysis be; the content aspect of the DG from improve product, the aspect that reduces the distillation load, the aspect that improves reaction efficiency consider, is preferably 2～60%, more preferably 3～50%, is preferably 5～50% especially, especially is preferably 10～50%.In addition; having carried out content after the esterification or that carried out the DG in the reaction oil behind the glycerolysis be; the content aspect of the DG from improve product, the aspect that reduces the distillation load, the aspect that improves reaction efficiency consider, is preferably 10～90%, more preferably 20～80%, is preferably 30～70% especially, especially is preferably 30～60%
In the present invention, reclaim lipid acid, glycerine, monoacylglycerol, and they are utilized again by distillation procedure.
In the present invention; consider from the content aspect that makes plant sterol from raw oil material remain in the aspect the grease and to increase DG; be necessary to make the content of the monoacylglycerol in the grease of distillation back to be in 0.5～15% scope; but preferred 0.5～10%; more preferably 0.5～8%; preferred especially 1～8%, especially preferred 1.3～8%.The weight of the cut that is recovered is difference according to reacting oil composition; but; the content of the monoacylglycerol from make distillation back grease is in 0.5～15% scope, increase the yield of DG, avoid using repeatedly the aspect of the amount of superfluous cut to consider; weight with respect to the composition beyond DG in the reaction oil and the triacylglycerol; be preferably 0.5～1.5 times; more preferably 0.6～1.4 times, preferred especially 0.6～1.2 times.In addition; remain in the aspect in the grease, the content aspect consideration that improves the DG in the product from making from the plant sterol the raw oil material; preferably making the monoacylglycerol content in the grease after the distillation is 0.03～0.8 with respect to the monoacylglycerol content in the reaction oil; more preferably 0.05～0.6, be preferably 0.1～0.5 especially.
In the present invention, consider from the aspect that reduces equipment cost and running cost, raising distillation ability, can select best distillation temperature, suppresses the increase of the trans unsaturated fatty acids that causes by hot resume and suppress thermal degradation when, the distillation condition preferred pressure is 2～300Pa, more preferably 3～200Pa is particularly preferably in 3～100Pa.Consider that from the increase aspect that suppresses trans unsaturated fatty acids temperature is preferably at 180～280 ℃, more preferably 190～260 ℃, preferred especially 200～250 ℃.Consider that from the increase aspect that suppresses trans unsaturated fatty acids the residence time is preferably at 0.2～30 minute, more preferably 0.2～20 minute, preferred especially 0.2～10 minute.Here, the so-called residence time, refer to the average retention time during grease reaches distillation temperature.
Among the present invention,, preferably above-mentioned pressure, temperature etc. are adjusted to, make the content of the monoacylglycerol in the grease after the distillation become 0.5～15% about distillation condition.In addition,, can enumerate and regulate the feeding flow, under the situation of using thin film evaporation unit, can also enumerate the methods such as thickness of regulating liquid film as other method that is adjusted in this scope.For example, under the common distillation condition under the situation of the content of the monoacylglycerol in the grease after the distillation discontented 0.5%, the preferred a kind of method that is selected from following method of using perhaps is used in combination the method more than 2 kinds that is selected from following method: (1) pressurize (reduction vacuum tightness); (2) reduce temperature; (3) increase the feeding flow; (4) thickness of increase liquid film under the situation of use thin film evaporation unit.More specifically; monoacylglycerol content in the grease under common distillation condition after the distillation is under 0.05～0.4% the situation; in order to make the monoacylglycerol content in the grease after the distillation reach 0.5～15%; preferably making pressure is generally 1.1～20 times; and/or reduce by 5～50 ℃ of temperature, and/or make the feeding flow be generally 1.1～10 times.
In the present invention, in order to make the stable purpose that waits of distillation procedure, before carrying out above-mentioned distillation, also can under low vacuum and/or low temperature, carry out fore-distillation to reaction oil.In addition, many when the amounts of glycerol in the reaction oil, when being separated into 2 liquid phases, preferably before carrying out above-mentioned distillation by liquid liquid lock out operation separation of glycerin phase.The part that these recovery part also can be used as reaction raw materials re-uses.
The condition of removing unreacted reactant and by product in common refining step is, pressure is 1～500Pa, temperature is 200～300 ℃, residence time is 1～10 hour, but, when being used in it in next reaction again after hot resume surplus, the recovery unreacting substance etc., the growing amount of trans unsaturated fatty acids will increase, and will be therefore not preferred.
In addition, as far as possible can the molecular distillation method that carry out not being arranged under the high vacuum of pressure 0.01～1Pa to the distillating method that grease is given hot resume.At this moment, can under the lower temperature of about 150～200 ℃ of temperature, implement, but owing to need high vacuum, it is big that the machine utilization of vacuum apparatus becomes, and processing power also reduces, and, also can be removed the useful trace ingredients of organism from the plant sterol of raw oil material etc., therefore not preferred.
Monoacylglycerol content in the grease after the distillation can be set according to the vapor-pressure curve of each composition at the distillation condition of 0.5～15% scope.The vapor-pressure curve here is meant the curve of expression material at each temperature vapour pressure.Preferred above-mentioned setting is in the temperature and pressure of the distillation process distillation residue (grease after the distillation) that (being the distillation process outlet during continuous still battery) the located finish time, between the vapor-pressure curve of monoacylglycerol and the vapor-pressure curve of DG.When under certain working pressure, distilling; preferably will add heat and be controlled to be, the vaporization temperature that the temperature of the distillation residue (grease after the distillation) of (being the distillation process outlet during continuous still battery) was higher than monoacylglycerol under this pressure when distillation process finished is lower than the vaporization temperature of DG under this pressure.In addition, also can use the vapor-pressure curve of each composition and vapor-liquid equilibrium relationship formula to carry out calculating, set distillation condition thus corresponding to the distillation of the form of institute's use water distilling apparatus.
Employed water distilling apparatus can be enumerated among the present invention, intermittently simple distillation device, batch fractionating device, continuous rectification apparatus, flash distillation plant, film type evaporation unit etc.In order to reach above-mentioned distillation condition, preferred film formula evaporation unit.The film type evaporation unit is to instigate distillating material to become film like and heat, and makes the evaporation unit of the form of cut evaporation.As the film type evaporation unit, according to film forming method can enumerate centrifugal thin film evaporation unit, flow down the Membrane-distillation device, knifing molecular distillation apparatus (Wiped film distillation) etc.Wherein, for fear of local superheating, prevent greasy thermal degradation when etc., preferably use the knifing molecular distillation apparatus.So-called knifing molecular distillation apparatus is to make distillating material stream become film like in the inboard of the generating surface of tubular, carries out film with slide and stirs, and make the device of cut evaporation from indirect heating.Hinder cost aspect, the aspect consideration of raising steam capability that reduces vacuum unit from reducing exhaust, preferred knifing molecular distillation apparatus is for carrying out the condensing form of cut with inner condensed device.Can enumerate " short stroke distillation (Short path distillation) device ", the Shinko Pantec Co. that UIC GmbH company makes, " the コ ソ ト ロ " that " the ヮ ィ プ レ ソ " that Ltd. makes, Hitachi make etc. as the knifing molecular distillation apparatus.
In the present invention, the cut that distillation is reclaimed is used as the part of next reaction raw materials again.The composition of recovery cut is difference according to reacting oil composition, but preferred monoacylglycerol is 5～80%, and lipid acid is 0.5～60%, and glycerine is 0.5～30% degree.Composition according to this recovery cut determines next to react the amount of needed raw material.Thereafter reaction conditions is preferably identical with the condition of last time.
In the present invention, from the generation of trans unsaturated fatty acids be suppressed and, can obtain plant sterol etc. effectively and consider from the remaining grease aspect of the composition of raw oil material, the aspect that can reduce the amount of waste, the cut that preferably will distill recovery is more than 2 times as the access times repeatedly that the part of next reaction raw materials re-uses.In addition, as the material that the part of next reaction raw materials is used, can be the cut that whole distillations is reclaimed, also can be the part of the cut of distillation recovery.The part of the cut that distillation is reclaimed is during as next reaction raw materials a part of, is preferably distillation and reclaims 50% or more of cut, discontented 100%, and is more preferably 60% or more, be discontented with 100%, preferred especially more than 70%, be discontented with 100%.Cut by will being distilled recovery re-uses as the part of next reaction raw materials, can reduce the amount of waste significantly, can become the little manufacturing process of carrying capacity of environment.Than situation about not re-using, the amount that preferably reduces waste is 1～100%, more preferably 5～90%, preferred especially 20～80%.
Further; the grease that contains DG on esterification that will be by lipid acid and glycerine or grease and the high density ground of the glycerolysis manufacturing of glycerine repeatedly mixes and when making oil and fat product; from the generation of trans unsaturated fatty acids be suppressed and, can obtain remainingly having plant sterol etc. to consider effectively from the grease aspect of the composition of raw oil material; the high density ground that preferably contains with good grounds the inventive method manufacturing contains the grease of DG more than 50%, more preferably more than 60%; preferred especially more than 70%, especially preferred 80～100%.
High density ground after the distillation contains the grease of DG; preferred then by known method distill, processing such as decolouring, deodorization are removed or decompose residual lipid acid, monoacylglycerol, coloring components, stink one-tenth and grade, to make with extra care.In addition; by from distilling the grease distillation DG that back or above-mentioned high density ground after refining contain DG; remove triacylglycerol and high boiling point composition as distillation residue, the high density ground of the concentration of the DG that can be further enhanced thus contains the grease of DG.At this moment, consider that preferably the triacylglycerol that will reclaim as distillation residue etc. directly or through refinement treatment re-uses as the part of reaction raw materials afterwards from the viewpoint that effectively utilizes raw material.
The grease that contains DG by the high density ground of the inventive method manufacturing; have when utilizing to the viewpoint of physiological functions such as intravital savings is few and consider as edible oil; preferably contain DG more than 40%, more preferably more than 50%, further preferred more than 60%, preferred especially 65～100%, especially preferred 80～98%.In addition, suppress to be fuming from as the local flavor of edible oil, heating the time, greasy productive aspect considers, preferably contains monoacylglycerol 0.05～7%; more preferably 0.07～6%; further preferred 0.08～4%, preferred especially 0.1～3%, especially preferred 0.2～2%.Further, consider, preferably contain plant sterol 0.1～1%, more preferably 0.12～0.9%, preferred especially 0.15～0.8% from aspect as the outward appearance of edible oil, physiologic effect, storage stability
[embodiment]
[analytical procedure]
(i) glyceryl ester is formed
In the sample bottle of glass, add about 10mg of sample and TMS agent (" silane-based agent TH " Northeast chemistry is made) 0.5ml, sealing, heating is 15 minutes under 70 ℃.Add water 1.5ml and hexane 1.5ml, and vibration.After leaving standstill, the upper strata is supplied with to gas chromatograph (GLC), glyceryl ester is formed analyzed.
(ii) constitute the composition of lipid acid
Add about 10mg of sample and 0.5mol/L sodium hydrate methanol solution 0.6ml in the sample bottle of glass, sealing was heated 30 minutes down at 70 ℃.Add boron trifluoride methanol reagent (the pure pharmaceutical worker's industry of boron trifluoride methanol complex compound methanol solution and light (strain)) 0.6ml again, sealing was heated 10 minutes down at 70 ℃.Add again chlorination saturated aqueous solution of sodium 1ml and and hexane 1.5ml, and the vibration.After leaving standstill, top section is dewatered with sodium sulfate (anhydrous), modulated fatty acid methyl ester.Its supply is analyzed to GLC.
(iii) plant sterol
Glyceryl ester composition with (i) is analyzed with identical with it method.
Embodiment 1 (enzyme process esterification)
[for the first time] 240 ℃ of temperature, through 3 hours reaction times high-pressure decomposing soybean oil, and pass the winter and obtain soya fatty acid.The glyceryl ester of the soya fatty acid that obtains formed and lipid acid is formed and represented with table 1 and table 2.With this soya fatty acid 1005g and glycerine 157g (FA/GLY=2), with immobilized lipase (the ノ ボ ザ ィ system ズ Lipozyme RM IM of society) 50g, carry out esterification at 50 ℃ of temperature, pressure 400Pa, the reaction times is 4 hours, separate immobilized enzyme, obtained esterification oil a.
This esterification oil a881g as distillating material, is used knifing molecular distillation apparatus (Shinko Pantec Co., Ltd.2-03 type, internal diameter 5cm, heat transfer area 0.03m
2) distill.Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the fat A 613g that recovery cut a ' is distilled removal.
[1 recirculation] will reclaim cut a ' 239g, soya fatty acid 871g, glycerine 123g (FA/GLY=2), with immobilized lipase (the same) 50g, carry out esterification at 50 ℃ of temperature, pressure 400Pa, the reaction times is 3 hours, separate immobilized enzyme, obtained esterification oil b.
This esterification oil b906g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease B631g that recovery cut b ' is distilled removal.
[2 recirculation] will reclaim cut b ' 220g, soya fatty acid 808g, glycerine 130g (FA/GLY=2), with immobilized lipase (the same) 50g, carry out esterification at 50 ℃ of temperature, pressure 400Pa, the reaction times is 3 hours, separate immobilized enzyme, obtained esterification oil c.
This esterification oil c909g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtain cut and be distilled the grease C639g that has removed.
The composition of the distillating material in table 3 each stage of expression and the result of the composition after the distillation.
Comparative example 1
By carrying out the operation that cut is used in recirculation, obtained esterification oil d (being equivalent to the esterification oil c in the operation of embodiment 1) with the identical method of method of record in embodiment 1.
This esterification oil d946g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is, 240 ℃ of heater heats temperature, and pressure 3.3Pa, feeding flow are 0.8 times of embodiment 1.Obtained the grease D538g that cut is distilled removal.The result is illustrated in the table 3.
[table 1]
| The composition of soya fatty acid [weight %] | |
| Glycerine | 0.0 |
| Lipid acid | 95.7 |
| Monoacylglycerol | 1.1 |
| DG | 2.3 |
| Triacylglycerol | 0.2 |
| Plant sterol | 0.17 |
[table 2]
| The composition [weight %] of the formation lipid acid of soya fatty acid | |||||||
| C14 | C16 | C16:1 | C18 | C18:1 | C18:2 | C18:3 | C20 |
| 0.1 | 2.7 | 0.1 | 0.7 | 28.1 | 60.6 | 7.3 | 0 |
[table 3]
| Real is executed example 1 | Comparative example 1 | ||||
| For the first time | 1 recirculation | 2 recirculation | 2 recirculation | ||
| Reaction oil | a | b | c | d | |
| Form [weight %] | Glycerine | 0.4 | 0.3 | 0.2 | 0.3 |
| Lipid acid | 13.4 | 14.3 | 15.5 | 15.1 | |
| Monoacylglycerol | 16.6 | 14.2 | 14.7 | 14.4 | |
| DG | 65 | 64.8 | 64.2 | 65.2 | |
| Triacylglycerol | 3.8 | 5.5 | 4.6 | 4.1 | |
| Plant sterol | 0.21 | 0.23 | 0.23 | 0.23 | |
| Grease after the distillation | A | B | C | D | |
| Form [weight %] | Glycerine | 0.0 | 0.0 | 0.0 | 0.0 |
| Lipid acid | 0.8 | 0.7 | 0.9 | 0.5 | |
| Monoacylglycerol | 3.1 | 3.5 | 6.2 | 0.3 | |
| DG | 89.8 | 87.7 | 86.3 | 91.2 | |
| Triacylglycerol | 5.7 | 7.5 | 5.8 | 7.5 | |
| Plant sterol | 0.08 | 0.13 | 0.20 | 0.02 | |
Embodiment 2 (chemical method glycerolysis)
[for the first time] uses the soybean oil of not taking off flavor as raw material.The glyceryl ester of employed soybean oil is formed and the composition of formation lipid acid is represented with table 4 and table 5.Among this soybean oil 500g and the glycerine 79g (FA/GLY=1.2), add potassium hydroxide 0.058g as catalyzer, carry out the glycerolysis reaction under 235 ℃ of temperature, normal pressure, the reaction times is 1 hour, add phosphoric acid 0.069g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil e.
This reaction oil e565g as distillating material, is used knifing molecular distillation apparatus (ShinkoPantec Co., Ltd.2-03 type, internal diameter 5cm, heat transfer area 0.03m
2) distill.Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease E314g that recovery cut e ' is distilled removal.
[1 recirculation] adds potassium hydroxide 0.058g as catalyzer in reclaiming cut e ' 206g, soybean oil 342g, glycerine 32g (FA/GLY=1.2), under 235 ℃ of temperature, normal pressure, carry out the glycerolysis reaction, reaction times is 1 hour, add phosphoric acid 0.069g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil f.
This reaction oil f568g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease F311g that recovery cut f ' is distilled removal.
[2 recirculation] adds potassium hydroxide 0.058g as catalyzer in reclaiming cut f ' 220g, soybean oil 329g, glycerine 30g (FA/GLY=1.2), under 235 ℃ of temperature, normal pressure, carry out the glycerolysis reaction, reaction times is 1 hour, add phosphoric acid 0.069g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil g.
This reaction oil g569g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtain cut and be distilled the grease G297g that has removed.
The composition of the distillating material in table 6 each stage of expression and the result of the composition after the distillation.
Comparative example 2
By carrying out the operation that cut is used in recirculation, obtained reaction oil h (being equivalent to the reaction oil g in the operation of embodiment 2) with the identical method of method of record in embodiment 2.
This reaction oil h454g is distilled with knifing molecular distillation apparatus (the same) as distillating material.Operational condition is 230 ℃ of heater heats temperature, pressure 1.3Pa.Obtained the grease H212g that cut is distilled removal.The result is illustrated in the table 6.
[table 4]
| Soybean oil composition [weight %] | |
| Glycerine | 0.0 |
| Lipid acid | 0.1 |
| Monoacylglycerol | 0.0 |
| DG | 1.3 |
| Triacylglycerol | 98.0 |
| Plant sterol | 0.32 |
[table 5]
| The composition [weight %] of the formation lipid acid of soybean oil | |||||||
| C14 | C16 | C16:1 | C18 | C18:1 | C18:2 | C18:3 | C20 |
| 0.1 | 10.4 | 0.1 | 4.5 | 24.6 | 51.7 | 7.1 | 0.4 |
[table 6]
| Real is executed example 2 | Comparative example 2 | ||||
| For the first time | 1 recirculation | 2 recirculation | 2 recirculation | ||
| Reaction oil | e | f | g | h | |
| Form [weight %] | Glycerine | 3.7 | 4.1 | 4.2 | 4.0 |
| Lipid acid | 0.1 | 0.2 | 0.2 | 0.2 | |
| Monoacylglycerol | 42.0 | 42.9 | 43.1 | 42.6 | |
| DG | 39.2 | 38.9 | 38.5 | 38.8 | |
| Triacylglycerol | 14.1 | 12.8 | 13.0 | 13.4 | |
| Plant sterol | 0.35 | 0.39 | 0.40 | 0.40 | |
| Grease after the distillation | E | F | G | H | |
| Form [weight %] | Glycerine | 0.0 | 0.1 | 0.1 | 0.0 |
| Lipid acid | 0.0 | 0.0 | 0.0 | 0.0 | |
| Monoacylglycerol | 7.9 | 5.2 | 5.1 | 0.47 | |
| DG | 66.4 | 69.9 | 68.4 | 74.1 | |
| Triacylglycerol | 25.0 | 24.1 | 25.6 | 24.9 | |
| Plant sterol | 0.16 | 0.18 | 0.20 | 0.02 | |
Embodiment 3 (chemical method esterification)
[for the first time] adds potassium hydroxide 0.050g as catalyzer in soya fatty acid 400g shown in table 1 and the table 2 and glycerine 101g (FA/GLY=2), under 235 ℃ of temperature, normal pressure, carry out esterification, reaction times is 1.5 hours, add phosphoric acid 0.059g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil i.
This reaction oil i452g as distillating material, is used knifing molecular distillation apparatus (ShinkoPantec Co., Ltd.2-03 type, internal diameter 5cm, heat transfer area 0.03m
2) distill.Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease 1278g that recovery cut i ' is distilled removal.
[1 recirculation] adds potassium hydroxide 0.050g as catalyzer in reclaiming cut i ' 146g, soya fatty acid 286g, glycerine 63g (FA/GLY=2), under 235 ℃ of temperature, normal pressure, carry out esterification, reaction times is 1.5 hours, add phosphoric acid 0.059g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil j.
This reaction oil j463g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease J246g that recovery cut j ' is distilled removal.
[2 recirculation] will reclaim among cut j ' 185g, soya fatty acid 259g, the glycerine 49g (FA/GLY=2) and add potassium hydroxide 0.050g as catalyzer, under 235 ℃ of temperature, normal pressure, carry out esterification, reaction times is 1.5 hours, add phosphoric acid 0.059g catalyst neutralisation after being cooled to below 100 ℃, obtained reaction oil k.
This reaction oil k464g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtain cut and be distilled the grease K249g that has removed.
The composition of the distillating material in table 7 each stage of expression and the result of the composition after the distillation.
Comparative example 3
By carrying out the operation that cut is used in recirculation, obtained reaction oil l (being equivalent to the reaction oil k in the operation of embodiment 3) with the identical method of method of record in embodiment 3.
This reaction oil 1448g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 1.3Pa.Obtained the grease L271g that cut is distilled removal.The result is illustrated in the table 7.
[table 7]
| Real is executed example 3 | Comparative example 3 | ||||
| For the first time | 1 recirculation | 2 recirculation | 2 recirculation | ||
| Reaction oil | i | j | k | l | |
| Form [weight %] | Glycerine | 1.8 | 2.9 | 2.8 | 1.7 |
| Lipid acid | 0.2 | 0.5 | 0.4 | 0.3 | |
| Monoacylglycerol | 35.6 | 42.5 | 41.8 | 33.8 | |
| DG | 43.2 | 39.4 | 40.1 | 43.3 | |
| Triacylglycerol | 18.4 | 13.7 | 14.1 | 20.1 | |
| Plant sterol | 0.16 | 0.19 | 0.20 | 0.15 | |
| Grease after the distillation | I | J | K | L | |
| Form [weight %] | Glycerine | 0.0 | 0.1 | 0.0 | 0.0 |
| Lipid acid | 0.0 | 0.0 | 0.0 | 0.0 | |
| Monoacylglycerol | 0.9 | 1.6 | 3.8 | 0.4 | |
| DG | 72.6 | 75.0 | 73.2 | 70.8 | |
| Triacylglycerol | 25.8 | 22.7 | 22.2 | 28.1 | |
| Plant sterol | 0.03 | 0.05 | 0.09 | 0.01 | |
Embodiment 4 (enzyme process glycerolysis)
[for the first time] is with the soybean oil 510g shown in table 4 and the table 5 and glycerine 80g (FA/GLY=1.2) and water 18g, be used as catalyzer lipase ay (manufacturing of amano enzyme goods Co., Ltd.) is fixed on the immobilized enzyme 30g on the ion exchange resin, under 40 ℃ of temperature, normal pressure, carry out the glycerolysis reaction, reaction times is 24 hours, separate immobilized enzyme, obtained reaction oil m.
This reaction oil m462g as distillating material, is used knifing molecular distillation apparatus (ShinkoPantec Co., Ltd.2-03 type, internal diameter 5cm, heat transfer area 0.03m
2) distill.Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease M243g that recovery cut m ' is distilled removal.
[1 recirculation] will reclaim cut m ' 176g, soybean oil 344g, glycerine 77g (FA/GLY=1.2) and water 18g, be used as catalyzer lipase ay (manufacturing of amano enzyme goods Co., Ltd.) is fixed on the immobilized enzyme 30g on the ion exchange resin, under 40 ℃ of temperature, normal pressure, carry out the glycerolysis reaction, reaction times is 24 hours, separate immobilized enzyme, obtained reaction oil n.
This reaction oil n481g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtained the grease N218g that recovery cut n ' is distilled removal.
[2 recirculation] will reclaim cut n ' 176g, soybean oil 342g, glycerine 80g (FA/GLY=1.2) and water 18g, be used as catalyzer lipase ay (manufacturing of amano enzyme goods Co., Ltd.) is fixed on the immobilized enzyme 30g on the ion exchange resin, under 40 ℃ of temperature, normal pressure, carry out the glycerolysis reaction, reaction times is 24 hours, separate immobilized enzyme, obtained reaction oil o.
This reaction oil o468g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 3.3Pa.Obtain cut and be distilled the grease O249g that has removed.
The composition of distillating material in each stage and the result of composition after the distillation have been represented in the table 8.
Comparative example 4
By carrying out the operation that cut is used in recirculation, obtained reaction oil p (being equivalent to the reaction oil o in the operation of embodiment 4) with the identical method of method of record in embodiment 4.
This reaction oil p480g as distillating material, is distilled with knifing molecular distillation apparatus (the same).Operational condition is 230 ℃ of heater heats temperature, pressure 1.3Pa.Obtained the grease P209g that cut is distilled removal.The result is illustrated in the table 8.
[table 8]
| Real is executed example 4 | Comparative example 4 | ||||
| For the first time | 1 recirculation | 2 recirculation | 2 recirculation | ||
| Reaction oil | m | n | o | p | |
| Form [weight %] | Glycerine | 0.9 | 1.6 | 1.1 | 0.8 |
| Lipid acid | 23.8 | 29.2 | 29.6 | 24.3 | |
| Monoacylglycerol | 16.3 | 15.2 | 15.6 | 16.1 | |
| DG | 36.2 | 33.7 | 32.4 | 36.2 | |
| Triacylglycerol | 21.6 | 19.2 | 20.3 | 21.6 | |
| Plant sterol | 0.27 | 0.24 | 0.23 | 0.25 | |
| Grease after the distillation | M | N | O | P | |
| Form [weight %] | Glycerine | 0.1 | 0.0 | 0.0 | 0.0 |
| Lipid acid | 0.8 | 0.4 | 3.8 | 0.3 | |
| Monoacylglycerol | 0.8 | 1.6 | 5.5 | 0.1 | |
| DG | 60.1 | 62.0 | 56.7 | 58.4 | |
| Triacylglycerol | 37.3 | 35.1 | 33.0 | 40.3 | |
| Plant sterol | 0.04 | 0.12 | 0.18 | 0.01 | |
As can be known: passing through enzyme process or the lipid acid of chemical method and the esterification of glycerine, under any situation of the glycerolysis of grease by enzyme process or chemical method and glycerine, compare with the resulting grease of reaction oil (for the first time) that distillation is initial, monoacylglycerol content in will the grease after distillation is when having carried out the recirculation of distillatory cut under 0.5～15% the condition and using, and the content of the plant sterol in the grease after the distillation increases; When having carried out distillation under the condition of the monoacylglycerol content in the grease after distillation discontented 0.5%, the plant sterol content in the grease after the distillation is few, and in addition, carry out recirculation this moment immediately, and the content of plant sterol can not increase yet.
Claims (8)
1. the greasy manufacture method that contains to a high density DG, make for the acyl group material be subjected to the acyl group substance reaction after, by fractionation by distillation unreacted reactant and by product, and the part of this distillation fraction as reaction raw materials re-used, it is characterized in that,
Monoacylglycerol content in the grease after the feasible distillation is 0.5～15 weight %.
2. high density as claimed in claim 1 ground contains the greasy manufacture method of DG, it is characterized in that,
Monoacylglycerol content in the grease after the feasible distillation is 0.5～10 weight %.
3. high density as claimed in claim 1 or 2 ground contains the greasy manufacture method of DG, it is characterized in that,
Monoacylglycerol content in the reaction oil is 2～60 weight %, and the monoacylglycerol content in the grease after the distillation is 0.03～0.8 with respect to the monoacylglycerol content in the reaction oil.
4. contain the greasy manufacture method of DG as any described high density ground in the claim 1～3, it is characterized in that,
For the acyl group material is the low-carbon-ester of triacylglycerol, lipid acid or lipid acid,
Being subjected to the acyl group material is glycerine.
5. contain the greasy manufacture method of DG as any described high density ground in the claim 1～4, it is characterized in that,
Is more than 2 times with described distillation fraction as the recirculation number of times that the part of reaction raw materials re-uses.
6. contain the greasy manufacture method of DG as any described high density ground in the claim 1～5, it is characterized in that,
At pressure 2～300Pa, 180～280 ℃ of temperature are distilled under the distillation condition of 0.2～30 minute residence time.
7. contain the greasy manufacture method of DG as any described high density ground in the claim 1～6, it is characterized in that,
Distill with the film type evaporation unit.
8. grease; use as any described high density ground in the claim 1～7 contains the greasy manufacture method of DG and makes, contain more than the DG 40 weight %, monoacylglycerol 0.05～7 weight %, plant sterol 0.1～1 weight %.
Applications Claiming Priority (3)
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| JP2005-133123 | 2005-04-28 | ||
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| US (1) | US7709667B2 (en) |
| EP (1) | EP1717318B1 (en) |
| KR (1) | KR101275403B1 (en) |
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| JP3569116B2 (en) | 1996-10-18 | 2004-09-22 | 花王株式会社 | Liquid general-purpose fat composition |
| US6261812B1 (en) * | 1997-08-18 | 2001-07-17 | Kao Corporation | Process for producing diglycerides |
| JP3847445B2 (en) | 1997-08-18 | 2006-11-22 | 花王株式会社 | Diglyceride production method |
| US6956058B2 (en) * | 2001-04-26 | 2005-10-18 | Kao Corporation | Method for improving insulin resistance |
| PL368137A1 (en) * | 2001-10-03 | 2005-03-21 | Archer-Daniels-Midland Company | Chemical process for the production of 1,3-diglyceride oils |
-
2006
- 2006-04-24 US US11/409,080 patent/US7709667B2/en active Active
- 2006-04-26 KR KR1020060037479A patent/KR101275403B1/en active IP Right Grant
- 2006-04-28 CN CN200610078177.9A patent/CN1854277B/en not_active Expired - Fee Related
- 2006-04-28 DE DE602006001891T patent/DE602006001891D1/en active Active
- 2006-04-28 EP EP06008870A patent/EP1717318B1/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027126A (en) * | 2008-05-29 | 2011-04-20 | 花王株式会社 | Method for producing fat or oil containing large amount of diacylglycerol |
| CN101768076A (en) * | 2008-12-30 | 2010-07-07 | 嘉里特种油脂（上海）有限公司 | Diglyceride and preparation method and application thereof |
| CN101768076B (en) * | 2008-12-30 | 2013-08-21 | 嘉里特种油脂（上海）有限公司 | Diglyceride and preparation method and application thereof |
| CN105400839A (en) * | 2009-08-19 | 2016-03-16 | 佳格食品股份有限公司 | Method for producing diglyceride by using by-product of table oil |
| CN102656257A (en) * | 2009-12-15 | 2012-09-05 | 花王株式会社 | Oil or fat composition |
| CN102656257B (en) * | 2009-12-15 | 2014-04-16 | 花王株式会社 | Oil or fat composition |
| US8884043B2 (en) | 2009-12-15 | 2014-11-11 | Kao Corporation | Oil or fat composition |
| CN102822327A (en) * | 2010-03-31 | 2012-12-12 | 花王株式会社 | Oil and fat composition |
| CN104131045A (en) * | 2014-08-08 | 2014-11-05 | 江西华敏粮油有限公司 | Method for preparing diglyceride |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1717318B1 (en) | 2008-07-23 |
| DE602006001891D1 (en) | 2008-09-04 |
| KR101275403B1 (en) | 2013-06-14 |
| CN1854277B (en) | 2013-01-09 |
| EP1717318A1 (en) | 2006-11-02 |
| US20060258872A1 (en) | 2006-11-16 |
| KR20060113447A (en) | 2006-11-02 |
| US7709667B2 (en) | 2010-05-04 |
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